In view of the problems associated with prior techniques such as dry or wet pressing and slip casting, thermoplastic injection molding has been increasingly used to form ceramic articles. Greenbodies prepared in this manner show much improved green strength. The process involves forming a ceramic greenbody by injecting into a mold a mixture of ceramic powder dispersed in a thermoplastic polymer that is held at a temperature above the softening point of the polymer. The mold is held at a temperature below the softening point of the polymer to solidify the mixture of powder and polymer in the mold. A typical ceramic powder/thermoplastic polymer mixture has a very high content of ceramic particles, typically from about 50 to about 87 volume %, and a minimum of the binder material.
The part is then removed from the mold and placed in a furnace to burn out the binder. The molded article is heated very slowly through the decomposition temperature of the polymer, e.g., at 10.degree. C./hour. The very slow heating is required to prevent deformation or "slumping" of the molded article once the furnace temperature exceeds the softening temperature of the polymer. Often, external physical support is needed to prevent slumping during the binder burnout step. Following the binder burnout step, the resulting porous greenbody is sintered, with concurrent shrinkage, to a dense ceramic part with the same shape as the molded object.
The use of an organic thermosetting resin as the binder for the ceramic particles has also been suggested. For example, U.S. Pat. No. 4,627,945 discloses injection molding of compositions that are cured in the mold by the addition of a curing agent to a mixture of ceramic powder and thermosetting phenolic resin binder. Thermoset molding has an advantage over conventional thermoplastic molding in that the greenbody is not prone to "slump" during the sintering process, since the thermoset binder, once cured, no longer has a softening point. The thermoset organic binder must, however, still be completely burned out of the molded article prior to the sintering step.
Reaction injection molding (RIM) has also been adapted for forming shaped ceramic greenbodies. U.S. Pat. No. 4,906,424 discloses a RIM process for molding a mix of ceramic powder and a polymerizable, low viscosity, multifunctional organic acrylate monomer or mixtures of monomers. The ceramic-monomer mixes are formulated to be highly filled, i.e., greater than 50 vol. %, with ceramic powder, yet have adequate fluidity to be processed at ambient temperature and readily injected into a hot mold. Useful monomers are those that are liquid at room temperature and can be polymerized to irreversibly solidify the fluid composition in the mold. The part is then ejected from the mold and subjected to subsequent post-curing, binder removal, sintering and, if needed, machining to produce a dense ceramic part.
However, organic binders such as polyacrylates must be burned out of the molded part in the process of converting the part to a dense, sintered ceramic article. The carbon-containing char that would otherwise remain in the sintered body would have a deleterious effect on the structural integrity and high temperature performance of the sintered part. Often, the carbon in the binders previously disclosed for RIM processes cannot be completely eliminated in the firing step. In addition, removal of an organic binder can cause structural defects in a sintered part due to voids formed from the rapid generation of volatile materials in the binder burnout step. A further complication arises in fabricating sintered parts of well-defined dimensions. Excessive shrinkage occurs when a high fraction of a ceramic greenbody must be removed in a binder burnout step. When the part finally densifies at high temperatures, dimensional distortion can be extreme, requiring a complex mold design.
Binder systems that contribute to the ceramic body ("non-fugitive" binders) have been used in traditional molding methods, although not in RIM processes. For example, U.S. Pat. Nos. 4,689,252; 4,722,988 and 4,772,494 disclose a crosslinkable silazane polymer that can be cured and subsequently pyrolyzed to convert the polysilazane to a ceramic material. The silazane polymer can be used for coating or impregnating a substrate, making ceramic fibers or as a sinterable binder for ceramic powders.
The prior art does not teach a method for (1) rapidly injection molding a high solids, non-dilatant dispersion of ceramic powder in a curable, liquid ceramic precursor at low temperature, i.e., a temperature less than about 120.degree. C., (2) subsequently curing the precursor and (3) sintering the molded article with concomitant conversion of the ceramic precursor binder to a ceramic.